Esters of drastically oxidized castor oil fatty acids with oxyalkylated phenol aldehyde resins



Patented Jan. 8, 1 952 ESTERS F DRASTICALLY OXIDIZED CAS- TOR OIL FATTY ACIDS WITH OXYALKYL- ATED PHENOL ALDEHYDE RESINS;

Melvin De Groote, St. Louis, and Bernhard Keiser, Webster Groves, M0., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application December 10, 1948,

Serial No. 64,461

The present invention is concerned with certain new chemical products, compounds or compositions, having useful applications in various arts. This invention is a continuation-in-part of particular value for resolving petroleum emul- 7 Claims. (Cl. 260-19) sions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in our co-pending application, Serial No. 726,215, 5 a more or less permanent state throughout the filed February 3, 1947 and now abandoned. It inoil which constitutes the continuous phase of cludes methods or procedures for manufacturthe emulsion. This specific application is deing said new products, compounds or composiscribed and claimed in our co-pending applications, as well as the products, compounds or tion, Serial No. 64,460, filed December 10, 19,48, compositions themselves. now Patent 2,541,997'issued February 20, 1951. Said new compositions are esters in which the See also our co-pending application, Serial No. acyl radical is that of the fatty acid of drasti- 64,469, filed December 10, 1948. cally-oxidized castor oil, and the alcoholic radi- The new products are useful as wetting, detercal is that of certain hydrophile polyhydric syngent and levelling agents'in the laundry, textile thetic products; said hydrophile synthetic prcdl5 and dyeing industries; as wetting agents and deucts being oxyalkylation products of (A) an tergents in the acidwashing of building stone alpha-beta alkylene oxide having not more than and brick; as wetting agents and spreaders in 4 carbon atoms and selected from the class conthe application .of asphalt in road building and sisting of ethylene oxide, propylene oxide, butylthe like; as a flotation reagent in the flotation ene oxide, glycide and methylglycide, and (3)20 separation of various aqueous suspensions conan oxyalkylation-susceptible, fusible, organic taining negatively charged particles such as sewsolvent-soluble, water-insoluble phenol-aldehyde age, coal washing wastewater, and various trade resin; said resin being derived by reaction bewastes and the like; as germicides, insecticides, tween a difunctional monohydric phenol and an emulsifying agents, as for example, for cosaldehyde having not over 8 carbon atoms and' metics, spray oils, water-repellent textile finishes;

reactive toward said phenol; said resin being as lubricants,etc'.' formed in the substantial absence of trifunc- For purpose of convenience'what is said heretional phenols; said phenol being of the formula inafter will be divided into three p st 1 will be concerned with the production of the OH resin from a difunctional phenol and an aldehyde; Part 2 will be concerned with the'oxy- R alkylation of the resin so as to convert it into a hydrophile hydroxylated derivative; and Part 3 will be concerned with the conversion of the imin which R is a hydrocarbon radical having at mediately aforementioned derivative into a total least 4 and not more than 12 carbon atoms and or partial ester. by reaction an acld an egter Substituted in the 2:45 position; Said oxyalkyl or other functional der1vat1v e, so as to obta1n a ated resin being characterized by the introduccompound of the t and tion into the resin molecule of a plurality of di- Subsequently described a valent radicals having the formula (R10)n, in 40 which R1 is a member selected from the class PART 1 consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radito the preParatlon of the phenokaldehyqe cals, and hydroxybutylene radicals, and n is a referePce 15 made to our co'pendmg apph" numeral Varying from 1 to 20; with the proviso cations, Ser1al Nos. 8,730 8,731, both filed that at least 2 moles of alkylene oxide be in February 161 1948 both of wh1ch are now aban" troduced for each phenolic nucleus; and with the e In E co'penfiing apphcations We final proviso that the hydrophile properties of scrlbed a fusible, orgamc solvent-soluble, watersaid oxyalkylated resin in an equal weight of Insoluble resm of the formula xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously OH H 0H I OH with one to three volumes of water. o 0- Although the herein described products have a H H number of industrial applications, they are of that it is 'tertafunctional. ience has been that, in resin manufacture and particularlyasidescribedherein, apparently oniy -one of the 'aldehydic ifunctions enters into the resinification' reaction. The inability of the other In such idealized representation n" is a numeral varying from 1 to 13 or even more, provided that the resin is fusible and organic solvent-soluble. R is a hydrocarbon radical having at least 4 and not over 8 carbon atoms. In the instant application B, may have as many as 12 carbon atoms, as in the case of a resin obtained from a dodecylphenol. In the instant invention it may be first suitable to describe 'the alkylene oxides employed as reactants, then the aldehydes, and

fication reaction or with the subsequent oxyalkylation of the resin; but the use of formaldehyde, inits'cheapest form ofan aqueous solution, for the production, of the, resins is particularly advantageous. 'Solid polymers of formaldehyde are more expensive and higher aldehydes both .lessvreactive, and are more expensive. thermore, the :higher ald'ehydes may undergo --other reactions which areznot desirable, thus in- Furtroducing difficulties. into .theresinification step.

- Thus acetaldehyde, for example, may undergo an aldol condensation, and it and most ofthe high- -er aldehydes'zeuter into self-:resinification when treated with strong acids or alkalies.

other hand, higher aldehydes frequently benefi- On the 'ciallyafiect the solubility and 'fusibility of aresin.

"This is illustrated, for example, by :the'clifferent characteristicsof the resin prepared from para- 'tertiaryxamylphenol and formaldehyde on one hand, and a comparable -product prepared from the same phenolic reactant and heptaldehyde on the other hand; Thejformer; as shown in certain "subsequent examples, is a hard, brittle, solid,

whereas the latter is soft and tacky, and obvi- 'ouslyeasier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydesmay be employed; particularly benzaldehyde. The employment of furfurals requires careful control for the reason that in addition to its aldehydic function, 'furfural can form condensations by virtue of its unsaturated structure. The production of resins from furiural for use in preparing products from the present process is most conveniently conducted "with weak alkaline catalysts and oftenwithalkali metal carbonates.

Usefullaldehydes, in addition to formaldehyde, fare acetaldehyde, propionic aldehyde, butyraldehyde, 2-ethylhexanal, ethyl-- butyraldehyde, heptaldehyde, and benzaldehyde, furfural and glyoxal. It would appear that the use :of glyoxal should be avoided due-to the fact However, our experaldehydic .function'to enter into the reaction is presumably due to steric hindrance. Needless to say, one can use a mixture of two or more aldehydes although usually this has'no advantage.

Resins of the kind, which are used as intermediates in this invention are obtained with the use of acid catalysts'or alkaline catalysts, or without the use of any catalyst at all. Among the useful alkaline catalysts are ammonia, amines, and quaternary ammonium bases. It is generally accepted thatwhen ammonia andamines. are employed as catalysts they enterinto the condensation reaction and, in fact, may operate by initial combination with the aldehydic reactant. The compound hexamethylenetetramine illustrates such a combination. In light of these various reactions it becomes difiicult to present any formula which would depict the structure of the various resins prior to oxyalkylation. More will be said subsequently as to the difference between the use of an alkaline catalyst and an acid catalyst; even in the use of an alkaline catalyst there is considerable evidence to indicate that the products are not identical where different basic materials are employed. The basic materials employed include not only those previously enumerated but also the hydroxides of the alkali metals, hydroxides oi the alkaline earth metals, salts in which R. is selected from the class consisting of hydrogen atoms and hydrocarbon radicals having at least carbon atoms and not more than 12 carbon atoms, with the proviso that one occurrence of R is the hydrocarbon substttuent and the other two occurrences are hydrogen atoms, and with the further provision that one or both of the 3 and 5 positions may be methyl substituted.

The above formula possible can be restated more conveniently in the following manner, to wit, that the phenol employed is of the following formula, with the proviso that R is a hydrocarbon substitutent located in the 2,4,6 position,

again with the provision as to 3' or 3,5 methyl substitution. This is conventional nomenclature, numbering the various positions in the usual clockwise manner, beginning with the hydroxyl position as one:

. and a difunctional phenol, i. e., a phenol in which one. of the three reactive positions (2,4,6) has been substituted by a hydrocarbon group, and particularly by one having at least 4 carbon atoms and not more than 12 carbon atoms, is well known. As has been previously pointed out, there is no objection to a methyl radical provided it is present in the 3 or 5 position.

These resins, used as intermediates to produce the products of the present invention are described in detail in ourPatent 2,499,370, granted March 7, 1950, and specific examples of suitable resins are those of Examples 1a through 103a of that patent, and reference is made thereto for a description of these intermediate resins and for examples thereof.

PART 2 Having obtained a suitable resin of the kind described, such resin is subjected to treatment with a low molal reactive alpha-beta olefin oxide so as to render the product distinctly hydrophile in nature as indicated by the fact that it becomes self-emulsifiable or miscible or soluble in water, or self-dispersible, or has emulsifying properties. The olefin oxides employed are characterized by the fact that they contain not over 4 carbon atoms and are selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide. Glycide may be, of course, considered as a hydroxy propylene oxide and methyl glycide as a hydroxy butylene oxide.

In any event, however, all such reactants contain the reactive ethylene oxide ring and may be best considered as derivatives of or substituted ethylene oxides. The solubilizing efifect of the oxide is directly proportional to the percentage of oxygen present, or specifically, to the oxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is 2:3; and in methyl glycide, 1:2. In such compounds, the ratio is very favorable to the production of hydrophile or surfaceactive properties. However, the ratio, in propylene oxide, is 1:3, and in butylene oxide, 1:4. Obviously, such latter two reactants are satisfactorily employed only where the resin composition is such as to make incorporation of the desired property practical. In other cases, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. They are usable in conjunction with the three more favorable alkylene oxides in all cases. For instance, after one or several propylene oxide or butylene oxide molecules have been attached to the resin molecule, oxyalkylation may be satisfactorily continued using the more favorable members of the class, to produce the desired hydrophile product. Used alone, these two reagents may in some cases fail to produce sufficiently hydrophile derivatives because of their relatively low oxygencarbon ratios.

Thus, ethylene oxide is much more effective than propylene oxide, and propylene oxide is more effective than butylene oxide.' Hydroxy propylene oxide (glycide) is more efiective than propylene oxide. Similarly, hydroxy butylene oxide (methyl giycide) is more eifective than butylene oxide. Since ethylene oxide is the cheapest alkylene oxide available and is reactive, its use is definitely advantageous, and especially in light of its high oxygen content. Propylene oxide is less reactive than ethylene'oxide, and butylene oxide is definitely less reactive than propylene oxide. On the other hand, glycide may react with almost explosive violence and must be handled with extreme care.

' The'oxalkylation of resins of the kind from which the initial reactants used in the practice of the present invention are prepared is advantageously catalyzed by the presence of an alkali. Useful alkaline catalysts include soaps, sodium acetate, sodium hydroxide, sodium methylate, caustic potash, etc. The amount of alkaline catalyst usually is between 0.2% to 2%. The temperature employed may vary from room temperature to as high as 200 C. The reaction may be conducted with or'without pressure, i. e., from zero pressure to approximately 200 or even 300 pounds gauge pressure (pounds per square inch). In a general way, the method employed is substantially the same procedure as used for oxyalkylation of other organic materials having reactive phenolic groups. I

It may be necessary to allow for the acidity of a resin in determining the amount of alkaline catalyst to be added in oxyalkylation. For instance, if a nonvolatile strong acid such as sulfuric "acid is used to catalyze the resinification reaction, presumably after being converted into a sulfonic acid, it may be necessary and is usually advantageousto add an amount of alkali equal stoichiometrically to such acidity, and include added alkali over and above this amount as the alkaline catalyst.

It is advantageous to conduct the oxyethylation in presence of an inert solvent such as xylene, cymene, decalin, ethylene glycol diethylether, diethyleneglycol diethylether, or the like, although with many resins; the oxyalkylation proceeds satisfactorily without a solvent. Since xylene is cheap and may be permitted to be present in the final product used as a demulsifier, it is our preference to use xylene. This is particularly true in the manufacture of products from low-stage resins, i. e., of 3 and up to and including 7 units per molecule."

If a xylene solution is used in an autoclave as hereinafter indicated, the pressure readings of course represent total pressure, that is, the combined pressure due to xylene and also due to ethylene oxide or whatever other oxyalkylating agent is used. Under such circumstances it may be necessary at times to use substantial pressures to obtain'effective results, for instance, pressures up-to' 300 pounds along with correspondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such as xylene can be eliminated in either one of two ways: After the introduction of approximately 2 or 3 moles of ethylene oxide, for example, per phenolic nucleus, there is a definite drop in the hardness and melting point of the resin. At this stage, if xylene or a similar solvent has been added, it can be eliminated by distillation (vacuum distillation if desired) and the subsequent intermediate, being comparatively soft and solvent-free, can be reacted further in the usual manner with ethylene oxide or some other suitable reactant.

Another procedure is to continue the reaction to c pletion with such solvent'present and then eliminate the solvent by distillation in the customary manner.

I Another suitable procedure is to use propylene oxide or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the powdered resin in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which represents the original resin dissolved in propylene emphasized, however, that theorganic solvent employed to indicate or assure that the. resin meets this requirement need not be'theone'used in oxyalkylation. Indeed, solvents which are susceptible to oxyalklation are included in this group of organic solvents. Examples of'such solvents are alcohols and alcohol-ethers. However, where a resin is soluble in an organic solvent, there are usually available other organic solvents which are not susceptible to oxyalkylation, useful for the oxyalkylation step. In any event-the organic solvent-soluble resin can be finely powdered, for instance to 100 to 200 mesh, and a slurry or suspension prepared in xylene or the like, and subjected to oxyalkylation. The fact that the resin is soluble in an organic solvent or the fact that it is fusible means that it consists of separate molecules. Phenol-aldehyde resins of the type herein specified'possess reactive hydroxyl groups and are oxyalkylation susceptible.

Considerable of what is said immediately hereinafter is concerned with ability to vary the hydrophile properties of the hydroxylated intermediate reactants from minimum hydrophile properties to maximum hydrophileproperties. Such properties in turn, of course, are effected subsequently by the acid employed for esterification and the quantitative nature of the esterification itself, i. e., whether it is total or partial. It may be well,"however, to point out'what has been said elsewhere in regard to the hydroxvlated intermediate reactants. See, for example, our copending applications, Serial Nos. 8,730 and 8,731, both filed February 16, 1948, and Serial No. 42,133, filed August 2, 1948, and Serial No. 42,134, filed'August 2, 1948', all four ofwhich are now abandoned. The reason is that the'esterification; depending on theacid selected; may vary the "hydrophile-hydrophobe'balance in one direction or the other, andalso invariably causes the development of'some property which makes it inherently different from the two reactants from which the derivative ester is obtained.

Referring to the hydrophile hydroxylated intermediates, even more remarkable and'equally difiicult'to explain, are the versatility and: the utility of these'compounds'considered'as chem ical reactants as one goes from minimumhydrophile'property to ultimate maximum hydrophile property. For" instance; minimum hydrophile property may be described roughly as the point where two ethyleneoxy radicals or 'moderatelyin excess thereof are introduced per'phenolichydroxyl. Such minimum hydrophi'lepropertypr sub-surface-activity or minimum surface activ ity means that the product shows-at least emulsis fyingproperties. or self-dispersion in cold or even in warm distilled water to 40 C.) in con centrationsof-0.5% -to.5.0-%. These materialsare generally, more soluble. in rcold-rwater. than warm iii water," andmay evenibe' very insoluble in boiling water. Moderately high .temperatures .aid.:ir'r-rezducing the viscosity of the solute under examination. Sometimes if one continues to shakexa hot olution, even though cloudy or containing an in:- soluble phase, one finds that solution takes place to give a homogeneous phase as the mixture cools. Such self-dispersion tests are conducted in the absence of an insoluble solvent.

When the hydrophile-hydrophobe balance is above the indicated minimum (2 mole of ethylene oxide per phenolic nucleus or the equivalent) but insuihcient to give a sol as described immediately preceding, then, and in that event hydrophile properties areindicated by the fact that one can produce an emulsion by having presout 10 to of an inert solvent such as xylene. All that one need to do is to have a xylene solution within the range of 50 to'90. parts byweight of'oxyalkylated derivatives and 50 to 10. parts by weight of xylene and mix such solution with one, two. or three times its volume of distilled water and shake vigorously so as to obtain'an emulsion which may be of the oil-in-water type or the water-in-oil type (usually the former) but, in any event, i due to the hydrophile-hydrophobe balance of the oxyalkylated derivative. We prefer simply to use the xylene diluted derivatives, which are described elsewhere, .for this test rather than evaporate the solvent and employ anymore'elabcrate tests, if the solubility is not sufllcientto permit the simple sol test in water'previously noted.

If the product is not readily water soluble it may be dissolved in ethyl or methyl alcohol, ethylene glycol diethylether, or diethylene glycol diethylether, With a little acetone added if required, making a rather concentrated solution, iorinstance 40% to 50%, and then adding enough of the concentrate-d alcoholic or equivalent solution to give the previously suggested 0.5% to 5.0% strength solution. Ifthe product is selfdispersing (i. e., if the oxyalkylated product is a liquid or a liquid solution self-emulsifiable), such 7 sol or dispersionv i referred to as at'least semistable in the. sense that sols, emulsions, or dispersions prepared are relatively stable, if they remainat least for some period of time, for instance 30 minutes to two hours, before showing any marked separation. Such tests are conducted at room temperature (22 C.). Needless to say, a test can be made in presence of an insoluble solvent such as 5% to 15% of xylene, as noted in previous examples. If. such mixture, i. e.,

F containing a water-insoluble solvent, is at least semi-stable, obviously the solvent-free product would be even more so. Surface-activity representing an advanced hydrophile-hydrophobe balance can also be determined by the use of conventional measurements hereinafter described. One outstanding characteristic property indicating surface-activity in a material is the ability. to formv a permanent foam in dilute aqueous solution, for example, less than 0.5%, when in the higher oxyalkylated stage, and to form an emulsion in thelowenand intermediatestages of .oxyalkylation.

Allowance must be made for the presence of a solvent in the final product in relation tothe hydrophile properties of the final product. The principle involved in the manufacture. of the herein contemplatedicornpounds. f or use .as .polyhydric reactants, is based on the con-version of ahydrophobe ornon-hydroph-ile compound. or

mixture of compounds into products which are distinctly hydrophile, at least to the extent that they have emulsifying properties or are selfemulsifying; that is, when shaken with water they produce stable or semi-stable suspensions, or, in the presence of a water-insoluble solvent, such as xylene, an emulsion. In demulsification, it is sometimes preferable to use a product having markedly enhanced hydrophile properties over and above the initial stage of self-emulsifiability, although we have found that with products of the type used herein, most eflicacious results are obtained with products which do not have hydrophile properties beyond the stage of self-dispersibility.

More highly oxyalkylated resins give colloidal solutions or sols which show typical properties comparable to ordinary surface-active agents. Such conventional surface-activity may be measured by determining the surface tension and the interfacial tension against parafiin oil or the like. At the initial and lower stages of oxyalkylation, surface-activity is not suitably determined in this same manner but one may employ an emulsification test. Emulsions come into existence as a rulethrough the presence of a surface-active emulsifying agent. Some surface-active emulsifying agents such as mahogany soap may produce a water-in-oil emulsion or an oil-in-water emulsion depending upon the ratio of the two phases, degree of agitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surfaceactive stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution i then mixed with 1-3 volumes of Water and shaken to produce an emulsion. The amount of xylene is invariably sufficient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsion so produced are usually xylene-in-water emulsions (oil-in-water type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a waterin-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol andformaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular Weight indicating about 4 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sufficiently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of thi test.

In manycases, there is no doubt as to the presence or absence of hydrophile or surfaceactive. characteristics in the polyhydric reactants in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (sub-surface-activity) tests for emulsi fying properties or self-dispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol 'formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reason, if it is desirable to determine the approximate point where self-emulsification begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylene-free resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another Way, it is really immaterial whether .a xylene solution produces a sol or whether it merely produces an emulsion.

In light of what has been said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as to the variation in the effectiveness of various alkylene oxides, and most particularly of all ethylene oxide, to introduce hydrophile character, it becomes obvious that there is a wide variation in the amount of alkylene oxide employed, as long as it is at least 2 moles per phenolic nucleus, for producing products useful for the practice of this invention. Another variation is the molecular size of the resin chain resulting from reaction between the difunctional phenol and the aldehyde such as formaldehyde. It is well known that the size and nature or structure of the resin polymer obtained varies somewhat with the conditions of reaction, the proportions of reactants, the nature of the catalyst, etc.

Based on molecular Weight determinations, most of the resins prepared as herein described, particularly in the absence of a secondary heating step, contain 3 to 6 or 7 phenolic nuclei with approximately 4 /2 or 5 /2 nuclei as an average. More drastic conditions of resinification yield resins of greater chain length. Such more intensive resinification is a conventional procedure and may be employed if desired. Molecular weight, of course, is measured by any suitable procedure, particularly by cryoscopic methods; but using the same reactants and using more drastic conditions of resinification one usually finds-that:higherrmolecular weights are; indicated ployed ina ifirst'stage, followed by neutralizationand addition of a small amount of acid catalyst in a second stage. It is generally believed that even in the presence of an alkaline catalyst, the number of moles of aldehyde, such as formaldehyde, must be greater than the moles of'phenol employed in order to introduce methylol groups in the intermediate stage. llhere is no indication that such groups appear in the final resin if prepared by the use of an acid catalyst. possible that such groups may appear in'the finished resins prepared solely with an alkaline catalyst; but we have never been able toconfirm this fact in an examinationof a large number of resins prepared by .ourselves. Our preference, however, is to use an acid-catalyzed resin, particularly employing a formaldehyde-to-phenol ratio of 0.95 to 1.20 and, as far as we have been able to determine, such resins are free from methylol groups. As a matter of fact, it is probable that in acid-catalyzed resinifications, the methylol structure may appear only momentarily at the very beginning of the reaction and in all probability is converted at once into a more complex structure during the intermediate stage.

One procedure which can be employed in the use of a new resin to prepare polyhydric reactants for use in the preparation of compounds employed in the present invention, is to determine the hydroxyl value by the Verley-Biilsing method or its equivalent. The resin as such, or in the form of a solution as described, is then treatedwith ethylene oxidein presence of 0.5% to 2% of sodium methylate as a catalystin stepwise fashion. The conditions of reaction, as far as time or per cent are concerned, are within the range previously indicated. Withsuitable agitation the ethylene oxide, if added in molecular proportion, combines within a. comparatively short time, for instance :a few minutes. to 2 to 6 hours, but in some instances requires as much as 8 to .24 hours. A useful temperature range is from 125 to 225 C. The completion-of the reaction of each addition. of ethyleneoxide in stepwise fashion is usually indicated by thereduction or elimination of pressure. An amount conveniently used for each addition. is generally equivalent to a mole or two moles of ethylene oxide per hydroxyl radical. When the amount of ethylene oxide added is equivalent to approximately 50% by weight of the original resin, a sample is tested for incipient hydrophile properties by simply shaking up in water as is, or after the elimination of the solvent if a-solvent is present. The amount of ethylene oxide used to obtain a useful demulsifying agent asa rule varies from 70% by weight of the original resin to as much as five or six times the weight of the original resin. In the case of a .resin derived frompara-tertiary butylphenol, aslittle as 50% by weight of ethylene oxide may give suitable solubility. With propylene oxide, even a greater molecular proportion is required and sometimes a resultant of only limited hydrophile properties it is 1 other insoluble solvent.

isobtainable. The same istrue :to even a greater extent with butyleneoxide. The hydroxylated. alkylene oxidesv are more effective in solubilizing properties than the comparable compounds-.- in. which no hydroxyl is present.

Attention is directed to the fact that in the subsequent examples reference is made to the: stepwise addition of the alkylene oxide, such as; ethylene oxide. It is understood, of course, there is no objection to the continuous addition of alkylene oxideuntil the desired stage of. reaction is reached. In fact, there may belessoi a hazard involved and it is often advantageous to .add the alkylene oxide slowly in a continuousv stream and in such amount as to avoid exceeding the higher pressures vnotedin the various examples. or elsewhere.

Itmay be well to emphasize the fact thatwhen resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is a comparatively soft. or pitch-line resin at ordinary temperatures. Such resinsbecome comparatively fluid at 110 to 165 C. as a rule, and thus can be readily oxyalkylated, preferably oxyethylated, without the. use of a solvent.

What has been said previously is .not intended to suggest that any experimentation. is necessary to determine the degree of oxyalkylatiom, and particularly oxyethylation. What has .beensaid previously is submitted primarily to emphasize the fact that these remarkable oxyalkylated resins having surface activity show unusual properties as thehydrophile character variesv from a minimum to an ultimate maximum. One should not underestimate the utility of any of these polyhydricv alcohols ma. surface-active or subsurface-active rangewithout examining them by reaction witha number of typicalesters herein described and subsequently examining theresultant for utility, either indemulsification or. in some other art or industry .as referred to elsewhere, or as a'reactantfor the manufacture of more complicated derivatives. A few simple laboratorytests which can be. conducted in .a routine manner will usually give all thev information that is required.

For instance, a-.simple rule to follow is to pre-- parea resin having .at least three phenolicnuclei and. being organic. solvent-soluble. Oxyethylate such resin, using. the. following four ratios of molesof ethylene oxide per phenolicunit equivalent: 2 to 1; 6 to l; 10 to 1; and 15 to 1. From a sample of each product remove any solvent that may be present, such'as xylene. Prepare.0.5.% and 5.0% solutions in distilled water,, as previously indicated. A mere examination of such series will generally revealan'approximaterange of minimum hydrophile character, moderate hydrophile character, and maximum hydrophile character. If the am 1 ratio does-not showminimumJhy'drGphile-Lcharacter by t'est'of'the so1ventfreerproductthen one should test its capacity to formyzan emulsionwhen admixed with xylene or If neither test 'showsthe required. minimum..hydrophile property, repetitionusing 2 to molesperphenolic nucleus will serve. Moderate hydrophile character should "be showmbyeitherthe 6 to 1 or 10 to 1 ratio. Such moderate hydrophile character is indicated by the factthat the sol in distilled water within the previously mentioned concentration range Isa permanent trans'lucentsol when viewed in-a comparatively thin layer, for instance the depth ofa testntube. Ultimatehydrophile character is usuassists.

ally shown at the 15 to 1 ratio test in that adding a small amount of an insoluble solvent, for instance 5% of xylene, yields a product which will give, at least temporarily, a transparent or translucent sol of the kind just described. The formation of a permanent foam, when a 0.5% to 5.0% aqueous solution is shaken, is an excellent test for surface activity. Previous reference has been made to the fact that other oxyalkylating agents may require the use of increased amounts of alkylene oxide. However, if one does not even care to go to the trouble of calculating molecular weights, one can simply arbitrarily prepare compounds containing ethylene oxide equivalent to about 50 to 75 by weight, for example 65% by weight, of the resin to be oxyethylated; a second example using approximately 200% to 300% by weight, and a third example using about 500% to 750% by weight, to explore the range of hydrophile-hydrophobe balance.

A practical examination of the factor of oxyalkylation level can be made by a very simple test using a pilot plant autoclave having a capacity of about to gallons as hereinafter described. Such laboratory-prepared routine compounds can than be tested for solubility and, generally speaking, this is all that is required to give a suitable variety covering the hydrophile-hydrophobe range. All these tests, as stated, are intended to be routine tests and nothing more. They are intended to teach a person, even though unskilled in oxyethylation or oxyalkylation, how to prepare in a perfectly arbitrary manner, a series of compounds illustrating the hydrophile-hydrophobe range.

If one purchases a thermoplastic or fusible resin on the open market selected from a suitable number which are available, one might have to make certain determinations in order to make the quickest approach to the appropriate oxyalkylation range. For instance, one should know (a) the molecular size, indicating the number of phenolic units; (1)) the nature of the aldehydic residue, which is usualy CH2; and (c) the nature of the substituent, which is usually butyl, amyl, or phenyl. With such information one is in substantially the same position as if one had personally made the resin prior to oxyethylation.

For instance, the molecular weight of the internal structural units of the resin of the following over-simplified formula:

R R n R (11:1 to 13, or even more) is given approximately by the formula: (Mol. wt. of phenol 2) plus mol. wt. of methylene or substituted methylene radical. The molecular weight of the resin would be n times the value for the internal limit plus the values for the terminal units. The left-hand terminal unit-of the above structural formula, it will be seen, is identical with the recurring internal unit except that it has one extra hydrogen. The right-hand terminal unit lacks the methylene bridge element. Using one internal unit of a resin as the basic element, a resins molecular weight is given approximately by taking (n plus 2) times the weight of the internal element. Where the resin molecule has only 3 phenolic nuclei as in the structure sirable products.

i4 shown, this calculation will be in error by several per cent; but as it grows larger, to contain 6, 9, or 12 phenolic nuclei, the formula comes to be more than satisfactory. Using such an approximate weight, one need only introduce, for example, two molal weights of ethylene oxide or slightly more, per phenolic nucleus, to produce a product of minimal hydrophile character. Further oxyalkylation gives enhanced hydrophile character. Although we have prepared and tested a large number of oxyethylated products of the type described herein, we have found no instance where the use of less than 2 moles of ethylene oXide per phenolic nucleous gave de- Examples it through 18b and the tables which appear in columns 51 through 56 of our said Patent 2,499,370 illustrate oxyalkylation products from resins which are useful as intermediates for producing the esterified products of the present invention, such examples giving exact and complete details for carrying out the oxyalkylation procedure.

The resins, prior to oxyalkylation, vary from tacky, viscous liquids to hard, high-melting solids. Their color varies from a light yellow through amber, to a deep red or even almost black. In the manufacture of resins, particularly hard resins, as the reaction progresses the reaction mass frequently goes through a liquid state to a sub-resinous or semi-resinous state, often characterized by being tacky or sticky, to a final complete resin. As the resin is subjected to oxyalkylation these same physical changes tend to take place in reverse. If one starts with a solid resin,

- than the original product from which it is made,

varying from a pale straw color to an amber or reddish amber. The viscosity usually varies from that of an oil, like castor oil, to that of a thick viscous sirup. Some products are waxy. The presence of a solvent, such as 15% xylene or the like, thins the viscosity considerably and also reduces the color in dilution. N0 undue significance need be attached to the color for the reason that if the same compound is prepared in glass and in iron, the latter usually has somewhat darker color. If the resins are prepared as customarily employed in varnish resinmanufacture, i.e., a procedure that excludes the presence of oxygen during the resinification and subsequent cooling of the resin, then of course the initial resin is much lighter in color. We have employed some resins which initially are almost water-white and also yield a lighter colored final product.

Actually, in considering the ratio of alkylene oxide to add, and we have previously pointed out that this can be predetermined using laboratory tests, it is our actual preference from a practical standpoint to make tests on a small pilot plant scale. Our reason for so doing is that we make one run, and only one, and that we have a complete series which shows the progressive effect of introducing the oxyalkylating agent," for instance,

reassess the ethyleneoxy "radicals. Our preferred procedure is at follows: We prepare a suitable resin, or for that matter, purchase it in the open market. we employ 8 pounds of resin and l pounds of xylene and place the resin and xylene in a suitable autoclave with an open reflux condenser. We prefer to heat and stir until the solution is complete. We have pointed out that soft resins which are fluid or semi-fluid can be readily prepared in various ways, such as'the use of orthotertiary amylphenol, ortho-hydroxydlphenyl, ortho-decylphenol, or by the use of higher molecular weight aldehydes than formaldehyde. If such resins aroused, a solvent need not be added but may be added as a matter of convenience or for comparison, if desired. We then add a catalyst, for instance, 2% of caustic soda, in the form of a% to 39% solution, and remove the water of solution or formation. We then shut oil the reflux condenser and use the equipment as an autoclave only, and oxyethylate until-a total of 60 pounds of ethylene oxide have been added, equivalent to 750% of the original resin; We prefer a temperature of about 150 C. to 12'5" C. We also talre samples at intermediate points as indicated in the'following table:

Pounds of Ethylene Oxide Added per E-pcund Batch Percentages eaesaes Sago Oxyethylation to 750% can usually be completed Within hours'and frequently more quickly.

The samples taken are rather small, for instance, 2 to 4: ounces, so that no correction need be made in regard tothe residual reaction mass. Each sample is divided in-two. One-half the sample is placed in an evaporating dish on the steam bath overnight so as to eliminate the xylene. Then 1.5% solutions are prepared from both series of samples, i; e., the series withxyl'ene present and the series with xylene removed.

Mere visual examination of any samples in solutionmay be sufficient to indicate hydrophile character 'orrsurface activity, i. e., the product'is soluble, forming acclloidal sol,- or the aqueous solution loams or shows emulsifying property. All these properties are related through adsorp-- tion at the interface, for example, a gas-liquidinterface or a liquid-liquid interfage. If desired, surface activity can be measured in anyone of the usual ways using a Du Nouy tensiometer or dropping pipette, or any other procedure for measuring interfaclal tension. Such tests are conventional and require no further description, Any compound having sub-surface-acitivity, and all derived from the same resin and 'oxyalkylated to a greater extent, i. e., those having a greater proportion of alkylene oxide; are useful for the practice of this invention.

Another reason why we prefer to use a pilot plant test of the kinda'oove described is that we can use the same procedure to evaluate tolerance towardsatrifunct-ional phenol such as hydroxybenzene ormetacresol satisfactorily. Previous ref enee' has beeirmaceto the that a 1 conduct a laboratory scale test which will cate' wlietl-ier' or not a resin, although soluble ni yields' arr insoluble rubber, that'is, an unsuitable t procedure roduce It is'obviou's that this pro of evaluating trifunotional phenol tolerance is more-suitable than the previous procedure.

It may be well to call attention to one result which-may be noted in a long drawn-out oxy alkylation; particularly oxyethyl'ation, whichwould notia pear in a normally conducted res-e tion'. Reference has been made to cross-linking and its eilect on solubility and also the fact that; if carried far enough, it causese incipient stringiness, then pronounced strin'giness, usually followed bya semi-rubbery or rubbery stage. Incipientstringiness, or even pronounced stringiness, or even'the tendency toward a rubbery stage, is not objectionable so long as'the final product is still hydrophile and at least sub-surface-active. Such material frequently is best mixed withapola r solvent; suchas 'alcohc'l or the like; and-preferably an alcoholic solution is used. Whichwe-wanttomake here, hoitever, is this": stringiness or rubb'erization at this stage may possibly bthe r'esult or "etherincation. Obviously if a' difunctional phenol and an aldehgrde roduce a non-cro'ss-linked resin molecule and if such molecule 'is oxyaikyl'ated so as to introduce a plurality of hydroxyl groups in each molecule; then and in-that event'if subsequent etherlfic'a tiontakes piace; one is'go'ing to obtain cross-linking. in the same general way that one would obtain cross-linking in other resinifi'caticn lea-c: tions.- Ordinarily-there is little or no tendency toward etherification during the oxyalkylation step. If it does take place at all, it is only to an insignificant and undetectable degree. However, suppose: that a certain weight of resin is treatedwith anequal weight of, or twice its weightof, ethylene oxide- This may be done in a comparatively short time, for instance, at or C. in 4 to 8 hours, or even less. On the other hand, if in an exploratory reaction, such as the kind previously described, the ethylene oxide were added extremely slowly in order totake stepwise samples, so that the 'reaction required eor 5 times as long to introducean equal amount of ethylene oxide employing the same temperature, then etheriiication might cause stringiness or a suggestion of rubberin'ess. For this'reason if in an exploratory experiment of the kind previously described there appears to be any stringiness or rubberiness, it maybe well to repeats the experiment and reach the intermediate stage-of oXya-lkylation as rapidly as possible and then proceed slowly beyond this intermediate stage. The entire purpose of this modified procedure is to cut down the time of reaction so as to avoid etherification if it be caused by the extended time period.

It may be well to note one peculiar reaction The point sometimes noted in the course of oxyalkylation', particularly oxyethylation, of the thermoplastic resins herein described. This eifect is noted in a case where a thermoplastic resin has been oxyalkylated, for instance, oxyethylated, until it gives a perfectly clear solution, even in the presence of some accompanying water-insoluble solvent such as 10% to 15% of xylene. Further oxyalkylation, particularly oxyethylation, may then yield a product which, instead ofgiving a clear solution as previously, gives a very milky solution suggesting that some marked change has taken place. One explanation of the above change is that the structural unit indicated in the following way where 812. is a fairly large number, for instance, 10 to20, decomposes and an oxyalkylated resin representing a lower degree of oxyethylation and a less soluble one, is generated and a cyclic polymer of ethylene oxide is produced, indicated thus: a

Her! I Hen This fact, of course, presents no difficulty for the reason that oxyalkylation can be conducted in each instance stepwise, or at a gradual rate.

and samples taken at short intervals so as to arrive at a point where optimum surface activity or hydrophile character is obtained if desired; for products for use in the practice of this invention, this is not necessary and, in fact, may be undesirable, i. e., reduce the efiiciency of the product.

We do not know to what extent oxyalkylation produces uniform distribution in regard to phenolic hydroxyls present in the resin molecule. In some instances,of' course, such distribution can not be uniform for the reason that we have not specified that the molecules of ethylene oxide, for example, be added in multiples of the units present in the resin molecule. This may be illustrated in the following manner:

Suppose the resin happens to have five phenolic nuclei. If a minimum of two moles of ethylene oxide per phenolic nucleus are added, this would mean an addition of moles of ethylene oxide, but suppose that one added 11 moles of ethylene oxide, or 12, or 13, or 14 moles; obviously, even assuming the most uniform distribution possible, some of the polyethyleneoxy radicals would contain 3 ethyleneoxy units and some would contain 2. Therefore, it is impossible to specify uniform distribution in regard to' the entrance of the ethylene oxide or other oxyalkylating agent. For that matter, if one were to introduce 25 moles of ethylene oxide there is no way to be certain that all chains would have 5 units; there might be some having, for example. 5 and 6 units, or for that matter 3 0r '7 units. Nor is there any basis for assuming that the number of molecules of the 'oxyalkylating agent added to each of the molecules of the resin is the same, or different. Thus, where formulae are given to illustrate or depict the oxyalkylated products, distributions of radicals indicated are to be statistically taken. We have, however, included specific directions and specifications in regard to the total amount of ethylene oxide, or total amount of any. other oxyalkylatingagent, to

' In regard to solubility of the resins and the oxyalkylated compounds, and for that'matter derivatives of the latter, the following should be noted. In oxyalkylation, any solvent employed should be non-reactive to the, alkylene oxide employed." This limitation doesnot ap- -Jly to solvents used in-cryoscopic determinations *or obvious reasons. Attention is directed to the act that various organic solvents may be employed to verify that the resin is organic solvent-soluble. Such solubility test merely characterizes the resin." The particular solvent used in such test may not be suitable for a molecular weight determination and,- likewise, the solvent used in determining molecular weight may not be suitable as a'solvent during oxyalkylation. For solution ofthe oxyalkylated compounds, or their derivatives at great-variety of solvents may be employed, such as alcohols, ether alcohols, cresols, phenols, ketones', esters, etc., alone or with the addition of water. Some of these are mentioned hereafter. We prefer the use of benzene or diphenylamine as' a solvent 'in making cryoscopic measurements' The most satisfactory resins are those which are solublein xylene or the like, rather than those which are soluble only in some other solvent containing elements other than carbon and'hy'drogen, for instance, oxygen or chlorine. Suchsolvents are usually polar, semi-polar, or'slightly polar in nature compared with'xylene', cymene,etc."

Reference to cryoscopic measurement is "concerned with theuse of benzene orother suitable compound as a solvent. Such method will show that conventional resins obtained, for example, from para-tertiary amylphenol and formaldehyde, inpresence of an acid catalyst, will have a molecular weight indicating 3, 4, '5 or'somewha't greater number "of structural units per molecule. If more drastic conditions of 're'sinific'ation' are employed or ifjsuch low stageresin is subjected toayacuum distillation treatment as previously described, one obtains a resin of a distinctly higher molecularweight. molecular weight determination used; whether cryoscopic measurement orotherwise, other than the conventional cryoscopic one employing benzene, should be checked .so as to insure tha fi ves' 9 sistent yalueson such 'conventional resins as a control. Frequently allthatisnecessary to make an approximation of the molecular weight range is to make a comparison with the dimer obtained by chemical, combination of two moles of the same phenol, and one mole of the same aldehyde under conditions to insure dimerization. As to the preparation of such dimers from substituted phenols, see Carswell, Phenoplastsf? page 31. The increased viscosity, resinous character, and decreased solubility, etc., of the higher polymers in comparison with the dimer, frequently are all that is required to establish that the resin contains 3 or more'structural unitspermolecule. I

Ordinarily, the oxyalkylation is carried out in autoclaves provided with agitators orstirring devices. We have found that the speed of the agitation markedly influences the time reaction. In some cases, the change from slow speed agitation, forexample, in a laboratory autoclave agitation with a stirrer operatingfat a speed of 19 .6:0":to20.0 R. '-P. *to'high speed agitation, with thestirrer-operatingat 250 1to 3501B. P. M., reduces the time required for voxyal-kylation by about one-half tO-YtWO-ithirdS. Frequently xylenesoluble products which give insoluble products by procedures employing .comparatively slow speed agitation, give suitable hydrophile :products when produced by similar procedure but with high speed agitation, .as .a :result. we believe, of the reduction in the :time IIoquired with consequent elimination or ourtailment of opportunity :for curing *of etherization. Even if ithe formation "Of an :insoluble product is :not involved, it is frequently advantageonstospeedhp the reaction, therebyreducing -production' time, by increasing agitating'speed. fInrlarge scale cpera-tionswehave demonstratedthateconomicaltmanufacturingresults from continuous 'oxyaikylation, that. is, an operation in whichfthe alkylene oxideis continuously fed to the.:reacticn':vessel, with rliigh speed agitation,i.-e.,;an agitator 'operating'at: 250-to 350 R. P. Continuous oxyalkylation, Other conditions being'the same-[is more "rapid thanbatch oxyalkylation, but "the latter is .ordinaxilyamore convenient for ilaboratoryoperation.

Previous reference hasbeen 'madeto the fact that in preparing esters or compounds of the kind herein "described, =particularly adapted for demulsificatlon :of water in-oil emulsions, and'for that matter for 1 other purposes, one shouldmake a complete exploration :of the wide variation in hydrophobe-hydrophile balance'as'preidously referred to. It has been stated, -furthermore, that this hydrophobe-"hydrophile balance of the oxyalkylated resins'is ."lmpartedasfar'as the range of variation goes, to a greater or lesser extent to "the herein 1 described -derivatives. FI-his means that one employing-the present inventionshould take the choice of the mostsuitablederi-vatire selected from a rnumber of representative com pounds, thus, not only should .a .varietyof resins be prepared exhibiting variety of .oxyalkylations, particularly oxyethylations, but .also .a variety of derivatives. This can be :done conveniently in lightof whathas beensaidpreviously. From a practical standpoint, using .pilot plant equipment, for instance, an .autoclave having a capacity of approximately three .to .five gallons. We havemade-a single .run byappropriate selections in which the molalratio of resin equivalent to ethylene oxide is one to one. 1 to 5, 1 to 10, 1 to 15, and 1 to 20. Furthermore, in making these particular runs we have .used continuous addition of ethylene oxide. In the continuous addition of ethylene oxide we have employed either a-cylinder of ethylene .oxide without added nitrogen, provided that the pressure of the ethyleneoxide was .sufliciently great to pass into the autoclave, or else We have used an arrangement which, in essence, was the equivalent of an ethylene oxide-cylinder with a means for injecting nitrogen so .as to .iorce out the ethylene oxide in the manner of anprdinary seltzer bottle, combined with the means for either weighing the cylinder or measuring the ethylene oxide used volumetrically. Such procedure and arrangement ,for injecting liquids is, of course, conventional. The following datasheets exemplify such operations, i. e., the combination of both continuous agitation and taking .samplesso as to give five difierent variants in oxyethylation. In adding ethylene oxide continuously, there isone precaution which must be taken at all times. The addition of ethylene oxide must stop immediately if there is any indication'that reaction is stopped or, obviously, if reaction is not started at'thebeginning of the reaction period. Since the addition of ethylene oxide is invariably an exothermic reaction, whether or not reaction has taken place can be judged in the usual manner by observing (a) temperature rise or drop, it any, (h) amount of cooling water or other means required to dissipate heat of reaction; thus, if there is a temperature drop without the use of cooling water or equivalent, or if there is no risein temperature without using coolin water control, careful investigation should be made.

In the tables immediately following, we are showing the maximum temperature and usually the operating temperature. In other words, by experience we have foundthat if the initial reactants are raised to the indicated temperature and then if ethylene oxide is added slowly, this temperature is maintained by cooling water until the oxyethylaticn is complete. We have also indicated the maximum pressure that we obtained or the pressure range. likewise, we have indicated the time required to inject the ethylene oxide as well as a brief note as to the solubility of the product at the end of the oxyethylaticn period. -As one period ends it will be noted we have removed part of the oxyethylated mass to give us derivatives, as therein described; the rest has been subjected to further treatment. All this is apparent by examining the columns headed Starting mix, Mix at end of reaction, Mix which is removed for sample, and Mix which remains as nextstarter.

The resins employedare preparedin the man-'- ner described in Examples 1a through 103a of our said Patent 2,499,370,--except'that instead of being prepared on a laboratory scale they were prepared in 10 to 15-gallonelectro-vapor heated synthetic resin pilot plant reactors, as manufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, and completely described in their Bulletin No. 2087 issued in 1947, with specific reference to'specification No. 71-3965.

For convenience, the following tables give the numbers of the examples of our said Patent 2,499,370 in which the preparation of identical resins on laboratory scale are described. It is understood that in the followin examples, the change is one with respect to the size of the operation. 7

The solvent used in each instance was xylene. This solvent is particularly satisfactory for the reason that it can be removed readily by 'distillation or vacuum distillation. In these continuous experiments the speed of the stirrer in the autoclave was 250 R. P. M.

In examining the subsequent tables it will be noted that if a comparatively small sample is taken at each stage, for instance, /2 'to'onegallon, one can proceed through the entire molal stage of 1 to 1 to 1 to 20, without remaking at any intermediate stage. This is illustrated by Example 10411.. In other examples we found it desirable to take a larger sample, for instance, a B-gallon sample. at an intermediate stage. As a result it was necessaryin such instances to start with a new'resin sample in order to prepare sufficient oxyethylated derivatives illustrating the latter stages. Under such circumstances, of course, the earlier stages which had been :previously prepared'were by-passed or ignored. This is illustrated in the tables where. obviously, it shows that the starting mix was not removed froma previous sample.

Date

Phenol for resin." Para-tertiary amylphenol i Aldehyde for'resin: Formaldehyde [Resin 'made in pilot plant size batch, approximately 25 pounds, corresponding to 3a of Patent'2,499,370 but this batch designated 104ml Mix Which is Mix Which Re- Starting Mix aigg fi g of Removed for mains as Next I Sample Starter Max. Max. Time 7 Pressure, Temp erahrs Solubility Ibls. gbs. Lbs lslbls. Ifibs. Lbs gbls. abs. Lbs lbls. kbs. Lbs

oes- 0- es- 0- es- 0- esvent in Eto vents in Eto vent in Eto vent in First Stage Resinto EtO v Molal Ratio 1:1 14.25 15.75 0 14. 15. 4.0 3.35 3.65 1.0 10. 9 12. 1 3.0 150 V4 I Ex. No. 104b.

Second Stage Resin to Et0 v Molal Ratio 1:5 10.9 12.1 3.0 10.9 12.1 15.25 3. 77 4.17 5.31 7. 13 7.93 9.94 70 158 $6 ST Ex. No. b

Third Stage Resin to EtO... 1 Molal Ratio 1:10- 7.13 7.93 9.94 7. 13 7.93 19. 69 3.29 3.68 9.04 3. 84 4.25 10.65 60 173 H; IS

EX. No. 1061)..."

Fourth Stage Resin to EtO.. Molal Ratio 1:15- 3.84 4.25 10.65 3.84 4.25 16.15 2.04 2.21 8.55 1. 80 2.04 7. 60 220 160 $6 I RS Ex. No. 1071)...

Fiftli Stage Resin to EtO Molal Ratio 1:20- 1. 80 2.04 7. 60 1. 80 2.04 10.2 100 150 -14 Q8 Ex. No. 108b.-

I=Insoluble. ST= Slight tendency toward becoming solublei FB Fairly soluble. RS Readily soluble. Q8: Quite soluble.

Phenol for resin: Nonylphenol Date Aldehyde for resin: Formaldehyde [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 7011 of Patent 2,499,370 but this batch designated 109a] v i Mix Which is Mix Which Re-" Starting Mix gg figg of Removed for mains as Next Sample Starter Max. Max. Tim Pressure, Temperahrs Solubility lbs. sq. in. ture, C. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs.

Lbs. Lbs. Lbs. Lbs. 501- Has Eto Sol- Res- Eto Sol- Res- Em Sol- 1165- Eto vent in vent in vent in vent in First Stage Resin to EtO Molal Ratio 1:1.-- 15.0 15.0 0 15.0 15.0 3 5.0 5.0 1.0 10.0 10.0 2.0 50 150 1% ST Ex. N0. 109b Second Stage ResintoEt0 Molal Ratio 1:5 10 10 2.0 10 10 9.4 2. 72 2.72 2. 56 7. 27 7.27 6.86 100 147 2 .DT Ex. No. 110b.

Third Stage Resinto EtO Molal Ratio 1:10 7. 27 7. 27 6. 86 7. 27 7. 27 13. 7 4.16 4. 16 7. 68 3. 15 3.15 5. 95 1% 8 Ex. No.111b

Fourth Stage Resinto Et0 Molal Ratio 1:15... 3. l5 3. 15 5. 95 3. 15 3. 15 8. 95 1. 05 1. 05 2. 95 2. 10 2. 10 6. 00 220 174 2% S Ex. No. 112b Fifth Stage Resin to EtO-.-. Molal Ratio 1 :20" 2. 10 2. 10 6. 00 2. 10 2. 10 8. 00 220 183 94 VS Ex. No. 113b- S=Soluble. ST=Slight tendency toward solubility. DT=Definite tendency toward solubility. VS =Very soluble.

memes 24 Date .Rh ljqpyggjn: PgrgmqtgLphenol Aldehyde fpr-.resin: Foimalde yde [3min 19. 1% pile; finfis ze ba ch, app x ma psn rrespo 1: o Ra n 2. 9. 0 u t s bam d si n ted 111 41 1 Mix Which is Mix Which Re- Starting M ix f g ggg Remoyed for mains asNnt V 1 Sample Starter 1. Max. Max. Time I Pressuiqe, Temgerahrs Solubility Lbs. Lbsu, Lbs. Lbs. Lbs. Lbs. Lbs.

Sol- Res- 3 5:8 Sol- Res- 83 jS i- -Res- .ggf Res- $3 vent in vent in ilent in in First Stage Resin to 11150. Molai atio 1;1 11,2 15.8 .51 14.2 15.8 ;3, 2 5 3. 1 3.4 9.75 11.1 12.4 72.5 150 1 ,4; 7 NB Ex. No.114b

Second Stage Resin to 111170-.-. I 1 Moiai liptio 11.1 12.4 11.1 12.4 1 2 .5 7.0 7.82 7.88 $1 4.58 4.62 1-71 16 88 Ex. No. b.-- M i Third su Resin to Et0 MoiaL-Rntio 1:10 6 64 7.36 1) :190 1% S Ex. No.116b

Fourth Stage Resin to Et0 Moial nations 4,40 4.9 :9 4.4 .400 160 M vs Ex. No. 1171).... 7

Fifth Stage Resin to EtO.- M01111 11 110 1:20.. 4.1 4.58 4.11 4.1 '260 172 ,4 vs Ex. N0. 118b 'l.-

9Mflg BN =NQt $19 1 ==9 WM9IHUI i 'sr 59. 11 Date Phenol for resin: M enthylphenol Aldehyde for resin. Formaldehyde [Resin made in pilot plant size batch, apnrbximately fi pounds; corresponding to 6911 of Patent 2,499,370 butthis batch designated 119a] Mix Which is Mix Which Re- Starting Mix gg figg of Removedjqr mains as Next Sample Starter v Max. Max. Time Pressure, Temp era- Solubility Lbs. Lbs. Lb y-Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbs 1915119- Pllrev 8 1-1 Res. fi s01. Ress 1- Res- Spl- Resvent in 1 went vent in vent in Firsi Stage Resin to EtO M0151 Ratio 1:1-.- 13.65 16.35 0 13. 65 16.35 3.0 9.55 11.45 2.1 4.1 4.9 0.9 80 1% NS Ex. No. 1190"...

Second Stage Resin to EtO M0131 Ratio 1:5-.. 10 12 0 10 12 10.75 4. 52 5.42 4.81 5.48 6.58 5.94 140 1%: S Ex. N9.120b

Third Stage.

Resin t0 EtO-'-.- Molai Ratio 1:10.. 5.48 6.58 5.94 5.48 6.58 10.85 90 160 V4 8 Ex. No. 1216"... v 1

Fourth Stage Resin to 13150. MolalRatioIzii. 4 l 4.9 0.9 4.1 4.9 13.15 180 171 1%: VS Ex. N0. 1221)"...

Fifth Stage Resin to EtO. Molal Ratio 1: 0.. 3.10 3.72 0.68 3.10 3. 72 13. 43 320 '34 VS Ex. N9. 12311...

S=Soluble. N S=Notsolu ble. YSaVerysolubie.

bate

. Aldehyde for resin: Formaldehyde [Resin made in pilot plant size batch, approximately 25pounds, eorrespondingto 2a of,Patent 2,499,870 but this batch designated 124a}:

Mix Which is Mix Which Re- Starting Mix fig fi g Removed ior mains as Next I v Sample Starter Max. Max. Tim; v I I Pressure, Temgera- Solubility 1 5 s. abs. Lbs Ibls. I bs. Lbs lsibls. Ifibs. Lbs Ibls. fibs. Lb W 9- 0- es- 0- eso- 1 es-. oesvent in Eto vent in Etc vent in Eco vent in Eto First Stage Resin to E50.... 7 M0181 Ratio 1:1- 14.45 15.55 0 14.45 15.55 i 4.25 5.97 6. 38 1. 75 8.48 9.17 2.50 150 M: 1 NS Ex. No. 124b. v

Second Stave ResintoEt0 V v Molal Ratio 1:5" 8.48 9.17 2.50 8.48 9.17 16.0 5.83 (i, 32 11.05 ,2. 2.85 4. 95 188 PS S8 Ex. No. b-

Third Stage Resin to Et0 F Molal Ratio1:10 4.82 5.18 0 4.82 5.18 14.25 400 183 Pi i S Ex. No. 12fib Fourth Stave Resin to EtO MolaLRatiohli- 3.85 4.15 0; 3.85 4. 15 17.0 120 as vs Ex. No. I275-.." 1

Fifth Stage ResintoEt0. MolalRatio1:20. 2.55 2.85 4.95 2. 55 2.35 15.45 so M: vs Ex. No. 128b D S =Solub1e. N S=Not soluble. SS=Somewhate soluble. VS=Very soluble.

Date Phenol for resin: -Menthyl Aldehyde for resin. :Propionaldehyde [Resin made on pilot plant size batch,epproximately 25 pounds, corresponding to 81 of Patent 2,499,370,11115 this batch designated 129s] Mix Which is Mix Which Re- Starting Mix f gg figg of Removed for mains as Next v Sample Starter Max. Max. Time Pressure, Temp era hm Solubility Ibls. 155. Lbs Ibls. Ifibs. Lbs 1 .5 5. es. Lbs 55. Lbs tum 1 0 eso eso es.- 0 esvent in Eto vent in Eto vent in E vent in Eto First Stage Resin to EtO. Molal Ratiohl-.. 12.8 17.2 12.8 17.2 2. 75 4.25 5.7 0.95 8.55 11.50 1.80 110 150 36 Not soluble. 1215351295.-. 5 w,

Second Stage Resin to Et0 t Molal Rati01:5 8.55 11.50 1.80 8.55 11.50 9.3 4.78 6.42 5.2 3. 77 5. 0S 4.10 .100 170 }6 Somewhat Ex. No. 1305..... 5 Y i soluble.

Third Stage Resin to E50- MolalRatio l: 3. 77 5. 08 4. 10 3. 77 5. 08 13. 1 100 182 M2 soluble. EX. N0. 131bv Fourth Stage Resin to EtO.. Mola] Ratio1:15 5.2 7.0 5.2 7.0 17.0 1 2.10 2.83. 6.87 200 182 M Vierysoluble- Ex. No.132b 5 I Fifth Stage Resin to EtO-..- Molal Ratio1:20 2.10 2.83 6.87 2.10 2.83 9.12 90 150 5 $6 D0. Ex. No. 133b l '1 Date ' Aldehyderfor rsin: Furfufial 7 1;... w'fii'eriis' Mix Whic hRe Starting Mix g ggg Removed fo'r' mains as Next' Sample Starter M I .W .L. .1 ax... Time ,1 I lgqessm e, "1311111518 his Solubility Lbs. Lbs. Lbs. Lbs. Dbsi Lbs; Lbs'. Lbs". L

Lbs. Lbs. Lbs Lbs. Sol- Res 501- Res- 561-. Res- 801-. Rs-

First Stage B95111 tO E19 q. 1 y M0121 Ratio 121;- 10.25 17.75 -I 10. 25.17. 2'5 2:65 4.60 [[65 7.6 13.16- I. 150 Ex. No. 1391)"...

Second Stage R in rEFO--- v a r MolallRatio 1:6" 716 13.15 1:85 7.6 13.15 9.35 6.2 9.00 6.40 2.4 4.15 1 2595 80 177 )6 Ex. Nd.'140b.

Third Stage Resinto Et0 H v 4 M0131 1131161210.. 4. 22 6. 98 4.22 6.98 10.01... 90 165 H 901111319 Ex. No. 141b Fourth Stage 3576 6.24 3.76 g 6.24 1 312 5 171" 4- i551, so'luble Fifth Stage Resin to Et.0 v j i 1 ,1 Molal RzitiblzZ 2.4 4.15 2.95 2.4 .15 11L7U i 90 )6 Do; Ex. No. 14317-.-

Date Phenol for reein: Pam-oetyl Aldehyde for resin: Fm-fw-alv [Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 422 of Patent 2,499,370 with 206 parts byweight of commerciel pera-octylphenol replacing 164 parts by weight of para-tertiary amyiphenol but this batch designated as 1442.]

Mix End of I Mix Which is Mix Which Re- Starting Mix Removed for mains as Next Ream Sample Starter Max M Pressure, Temperahm Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Sol- Res- 1??? Sol- Resfig- So1- Res- Ega- B01- Res- Eggvent in vent; in vent in vent in First Stage Resinto EtO- i I M0181 Ratio 1: 12 1 18.6 12.1 18.6 3.0 5.38 8.28 1.34 6. 72 10.32 1.66 80 150 H: Insoluble. Ex. No. 1445.-.

Second Stage I v V Slight tend- Reainto EtO-. V I f 1 ency to- Molal Ratio1:5. 9.25 14.25 9.25 14.25 11.0 3. 73 5.73 4.44 5.52 8.52 6.56 100 177 212 ward be- Ex.No.145b coming 1 soluble.

Third Staqe ResintoEtO Molal 12812101210 6. 72 10.32 1.66 6.72 10.32 14.91 4.97 '7. 62 11.01 1.75 2.70 3.90 85 182 M Eflirly solu- Ex. No. 1465"... Die.

Fourth Stage Resinto EtO v Mo1alRatio1:15..}5 52 8.52 6.56 5.52 8.52 19.81 100 176 ,4 Readilysolu- Ex. No. 1475... his.

Fifth Stage ResintoEtO v Mo1alRatio1:20 1.75 2.70 3.90 1.75 2.70 8.4 80 160 $4 Quite solu- Ex. No. 1486"-.. ble.

Date Phenol fo r resin: Para-phenyl Aldehyde for resin: Furfural [Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 42a of Patent 2,499,970 with 170 parts 11y weight of commercial paraphenylphenol replacing 164 parts by weight of para-tertiary amylphenol but this batch designated as 14911.]

Mix Whieliis Mix Which Re- Starting Mix fig fi g Removed for mains as Next 0 Sample Starter Max I Pressure, Temp erafi Solubility Ibls. 15. Lbs 'I b s. abs. Lbs 1 1 s. 115. Lbs 1 1 s. fibs. Lbs f f 0- es- 0- es- 0-. es- 0- esvent in Eto vent in Eto vent in Eto vent in Eto First Stage ResintoEtO. Molal Ratio 1:1 13 9 16.7 13.9 16.7 3.0 3.50 4.25 0.80 10:35 12.45 2.20 100 160 16 Insoluble. EX. N0. 1495.-.

Second Stage Resin to mom. Bligh Moial Ratio 1:5-.- 10.35 12. 45 2.20 10.35 12. 4s 12.20 5.15 6.19 6.06 5.20 6.26 0.14 r so 183 3, 3: ELNO 1505".-. biiity. Third Stage ResintoEtO M0181 Ratio 1:10-- 8 90 10.7 8.90 10.70 19.0 5. 6.38 11. 32 3.60 4. 32 7.68 H 193 M: Fairly solu- Ex. No. 1515-.." I I Die.

Fourth Stage ReslntoEt0- Moial Ratio 1:15.. 5 20 6.26 6.14 5.20 6.26 16. 171 )6 Readily 50l- Ex. No. 152b uble.

Fifth Stage I Resin to E10- Sam pie somewhat rubbery and gels ggg zg gg :fk} 3 60 60 68 tlnomls but fairly soluble l 230 2 j Mole Batiq 1:20..

Starting Mix Second Smge I I I 'Rsin 1561 550 i 1 5 E 1 MdlalTRatio 1. 2.80 3.64 160 I 18 $4 IJ SOllibIe. Ex. No. 159b; i

Th ird Stage Resin to Et0 Mplal Ratio 1:10 ExJNo'.

Fourth Staie Resin 1.6mm"- Fifth Stage a I Resin to Eton" I 3 Date [Resin made on pilot plantsize batch, approximately 25 para-secondary butylphenol replacing 164 pa Phenol for resin: Para-secondary butylphenol Aldehyde for resin: Furfural Mix Which is Mix Which Re- Starting Mix figg fi g of Removed for mains as Next Sample Starter Max Max Time llgressure, gemp eiihm Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Sol- Res- 5?? 801- Resg ga- Sol- Res- 23- 801- Resga vent in vent in vent in vent in First Stage Resin to Et0 Molal Ratio 1:1-- 12.0 17.9 12. 0 17.9 3. 5 2. 65 3.98 0.77 9.35 13.92 2. 73 150 171 L6 Insoluble. Ex. No. 161b Second Stage Slight tend- Resinto EtO- ency to- Molal Ratio 1:5 9.35 13.92 2. 73 9.35 13. 92 13. 23 5.00 7. 42 7.08 4.35 6.50 6.15 100 192 1% Ward be- Ex. No. 162b coming scluble. Third Stage Resin to Et0... Molal Ratio 1:10 6.25 8.95 6. 25 8.95 17.0 3. 23 v 4. 6] 8.76 3.02 4.34 8.24 120 188 542 Fairly solu- Ex. No. 1635"... his.

Fourth Stage Resin to EtO MOlal Ratio 1:15 4.35 6. 50 6.15 4. 6.50 18.40 100 181 X; Readily l- Ex. No. 164b uble.

Fifth Stage Resin to EtO. Sample somewhat rubbery and gelat- Molal Ratio 1:20. 3.02 4.34 8.24 3.02 4.34 16.49 inous but shows limited water 501- 120 161 -34 Ex. No. 1651).... ubillity. I

Date

[Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 34a of Patent 2 para-octylphenol replacing 164 parts by weight of para-tertiary amylphenol but Phenol for resin: Para-octylphenol Aldehyde for resin: Propionaldehyde ,499,370 with 206 parts by weight of commercial this batch designated as 16611.]

- Mix Which is Mix Which Re- Starting Mix MIX at End of Removed for mains as Next Reactlon Sample Starter Max Max Time Pressure, flemp erahrs. Solubility lslbls. Ifibs. Lbs l'bls. Ifibs. Lbs llbls. fibs. Lbs Isbls. bs. Lbs

o eso eso es- 0 esvent in Eco vent in Eto vent in Eto vent in Eto First Stage Resin to EtO Molal Ratio 1:1... 13. 3 16.9 13.3 16. 9 3.0 3. 1 4. 0 0.70 10. 2 12.9 2.3 100 150 $6 Insoluble. Ex.N0.166b

Second Stage ResintoEtO Molal Rati01:5 10.2 12.9 2.3 10.2 12.9 11.3 6.34 8.03 7.03 3.86 4.87 4. 27 100 166 $4 Becoming Ex. No. 1675"". soluble.

Third Stage Resin to Et0 Molal Ratio1:l1.3 6546 8. 24 6. 46 8. 24 16.5 3. 52 4. 49 8. 99 2. 94 3. 7. 51 177 $4 Fairly solu- EX. No.168b "blc. Fourth Stage Resin to EtO- Molal Ratio'lzlE... 3. S6 4. 87 4. 27 3.86 4. 87 13. 02 80 204 M Readily sol- Ex. No. 1695... uble.

Fifth Stage Resin to E.o.;.. Molal Ratio1:20.. 2.94 75 7.51 2. 94 3.75 13.26 Soluble. vEx. No.170b

Date Phenol for resin: Pam-nonylphenol Aldehyde for res-in: Propionaldehyde {Resin made on pilot plant size batch, approximately 25 pounds, corrwponding to 8241 of Patent 2,499,370 but this batch designated as 171'} Mix Which is Mix W'hich Re- Starting Mix figg figg of Removed for mains as Next Sample Starter Max. Max. Time Pressure, Temp erahm Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs.

Lbs. Lbs. Lbs. Lbs. Sol- Res- Eto Sol- Res- Eco Sol- Res- Eto Sol- Rcs- Eto vent in vcnt in vent in vent in i First Stage Resin to EtO. Molal Ratio 1:1... 10. 9 18.0 10. 9 18. 3. 0 2-. 65 4. 4 0. 75 8. 25 13. 60 2. 25 120 150 $42 Insoluble. Ex. No. 1715.....

Second Stage Resin to EtO. Molal Ratio 1: 8. 25 13. 60 2. 25 8. 25 13. 60 11. 50 5. 8. 35 7. 05 3. 5. 4. 45 95 174 56 Becoming Ex. No. 17212.. soluble.

Third Stage Resin to EtO. Molal Ratio 1:10-- 5. 65 9. 5. 65 9. 35 15. 75 3. 71 6.14 10. 35 1. 94 3. 21 5. 00 182 71: Fairly Ex. No. 1731;. soluble.

Fourth Stage Resin to EtO.. M01a1R-atio1:15. 3.15 5.25 4. 3.15 5.25 13.45 B5 182 V5 Readily Ex. No. 17417.. soluble.

Fifth Stage Resin to EtO. Molal Ratio 1:20-. 1. 94 3.21 5. 40 1.94 3. 21 10. 90 150 $5 Soluble. Ex. No. 1756... i

Date Phenol for resin: Para-tertiary amylphenol Aldehyde for resin: Propionaldehyde {Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 34a of Patent 2,499,370 but this batch designated as 17612.]

Mix Which is Mix Which Re- Starting Mix figg figg Removed ior mains as Next Sample Starter Max. Max. Time Pressure, Tem erahrs Solubility gbls. gbs. Lbs l bls. gos. Lbs gb s. gbs. Lbs gbls. Lbs. Lbs

o esno eso eso Resvent in Eto vent in Eto vent in Em vent in Eto First Stage fRe-sinto EtO--.. r p 7 Molal Ratio 1:1... 12. 6 16. 2 12. 6 16. 2 3. 5 3.08 3. 96 0. 86 9. 52 12.24 2. 64 105 150 Hz Insolublc. Ex. No. 176D"-.-

Second Stage Resin to Et0 I Molal Ratio 1:5 9 52 12. 24 2. 64 9. 52 12. 24 12. 89 5. 27 6. 79 7.14 4. 25 5. 45 5. 171 56 B c c 0 m 111;; Ex. N o. 1775. soluble.

Third Stage Resin to 15130. I Molal Ratio 1. 8. 3 6. 5 8.3 17. 75 3. 81 4.87 10. 42 2. 69 3. 43 7. 33 120 183 A; Fairly 5011 Ex. No. 1785..... ble.

Fourth Stage Resin to EtO. Molal Ratio 1:15.- 4. 25 5. 45 5. 75 4. 25' 5. 45 17. 25 85 196 $6 Readily s01- Ex. No. 1795.- uble.

Fifth Stage Resin to EtO.... Molal Ratio 1:20.. 2.69 3. 43 7. 33 2. 69 3. 43 14. 55 160 in; Soluble. Ex. No. 1801)... 5 PART 3 ganese ricinoleate, etc., or it may be of the organic It is well known that oxidized oils can be obtained from castor oil, ricinoleic acid, and various derivatives of ricinoleic acid, such as monoricinolein, diricinolein, and pclyricinoleic acids. They are produced by the common practice of blowing or oxidizing castor oil and similar fatty oils or acids, particularly non-drying, unsaturated fatty oils, by means of a gaseous medium, such as air, oxygen, ozone, or ozonizcd air. The gaseous medium, such as air, may be moist or dry, and the oxidation may take place in the presence of a catalyst. The catalyst may be of a metallic type, such as lead ricinoleate, cobalt ricinoleate, mantype, which produces peroxide such as alphapinene, linseed oil, etc. Oxidation may take place at atmospheric pressure or superatmospherlc pressure, 1. e., pressures up to or including 200 pounds gauge pressure, at any temperature slightly above the boiling point of water, for instance, 0., up to any temperature which does not produce undue decomposition by pyrolytic reaction.

The time of blowing may be fairly brief, for example, 810 hours, or it may be quite extensive, for instance, as long as 10-12-14 days, the longer time periods being employed generally when the tively small modifications of certain important indices, such as the iodine value, the acetal value, and the saponification value. If drastic oxidation takes place, either by continued mild oxidation or by more vigorous oxidation from the very beginning of the reaction, as induced by either a higher reaction temperature or the presence of a catalyst, then there is obtained an oxidized oil having characteristics which clearly indicate that drastic oxidation has taken place. These indices of drastic oxidation are of a relatively low iodine value, such as 70 or less, and may be as low as 40, or thereabouts; a saponification value of 215 to 283, or thereabouts; an acetyl value of approximately 160-200; an increased viscosity such as the material may be hardly mobile at ordinary temperatures; a specific gravity of almost one, or a trifle over one at times; an increased refractive index; and, in the absence of other coloring matter, a yellow to deep orange color. The color at times may be a questionable index, since some oxidized castor oils are bleached to make them particularly adaptable for use as plasticizers, in light colored resinoid bodies.

Drastically-oxidized castor oil can be prepared by well known methods, or such products can be purchased in the open market under various trade names, such as blown castor oil, blended castor oil, oxidized castor oil, "heavy castor oil, viscous castor oil, etc. These various trade names appear to be applied to drastically-oxidized castor oils which differ merely in degree but not in mind.

The color of these oils is still pale or lightcolored, in comparison with the oil from which they have been derived. Usually they are fairly transparent, particularly in reasonably thin layers, for instance, an inch or less. Such oils represent .greater or lesser degrees of partial oxidation in the sense that there is a drastic change, in comparison with the change that takes place when a film of castor oil is exposed to air.

For the sake of differentiation, oils of the kind previously described will be referred to as pale blown, drastically-oxidized castor oils; and the same terminology is intended to apply to all other ricinoleic bodies of the kind hereinafter described.

In addition to pale blown, drastically-oxidized castor oil, there is also another type of the kind described in U. S. Patent No. 2,023,979, to Stehr, dated December 10, 1935. The product described in said Stehr patent is characterized by the fact that drastic oxidation is continued past the stage where a pale blown oil is obtained, and where, as a matter of fact, a superoxidized product of almost semi-livery consistency is obtained.

Such products are usually much darker in color than the pale blown castor oils, for the reason that certain side reactions occur with the formation of dark colored by-products, and as a result the transparency of the oil has greatly decreased or disappeared, and it is apt to be opaque in nature.

Attention is directed particularly to U. S. Patent No. 2,183,487, dated December 12, 1939, to Colbeth,

to the extent that it discloses details as to the .volatilization of the same.

38 oxidation of castor oil in a manner that is particularly desirable.

Our preference is to employ a pale blown castor oil of the following characteristics:

Acid number 15.1 to 25.0 Saponification number 230.5 to 274.0 Iodine number 43.5 to 55.0

Acetyl number 164.0 to 192.0 Hydroxyl number 188.0 to 220.0 Per cent Luisaponifiable matter 1.0 Per cent S03 0.0 Per cent ash -1 Trace Reactions intended to introduce the acid radicals of blown castor oil into the oxyalkylated resin compound of the kind previously described, may involve procedures analogous to those described in our co-pending application, Serial No. 64,454, filed December 10, 1948, now Patent No. 2,541,995 issued February 20, 1951. For instance, one may obtain the fatty acids in the usual manner, that is, by acid saponification, or by alkaline saponification, followed by oxidation. One may react such fatty acids with a low molal alcohol, such as methyl or ethyl alcohol and produce esters by the elimination of such alcohol. However, acidification, either in the course of acid saponification, or in the course of acidification, after alkaline saponification, produces at least some significant changes in the general character of the blown oil radicals, and thus, we much prefer to use a procedure in which ester formation takes place without going through an acid stage.

One procedure is to subject such drastically blown castor oil to methanolysis or ethanolysis. In such particular procedure a glycerol layer is separated and the methyl or ethyl esters obtained with acidification. Such procedure is commonly employed, particularly in producing certain polymeric fatty acid esters. For example, see U. S. Patent No. 2,384,443, dated September 11, 1945, to Cowan and Teeter. Briefly then, a'very desirable procedure involves methanolysis or ethanolysis to produce the methyl or ethyl ester, and then involves the usual reaction so as to volatilize'alcohol. Then again correspondsto the general 'descriptionappearing in our aforementioned co-pending application, Serial No. 64,454,

filed December 10, 1948. 3 Our second preferred procedure involves crossesterification with the drastically blown castor oil with the liberation of glycerol and without the All such procedures for the production of esters are conventional and require no further description. They will be illustrated, however, by examples.

Example 10 by the Verley-B'o'lsing method, or any other acceptable procedure. The esterification reaction is conducted in any conventional manner, such as that employed for the preparation of the higher fatty acid ester of phenoxyethanol.

Fatty acids, and particularly unsaturated fatty acids, show at least some solubility in the oxyalkylated derivatives of the kind shown in the previous examples, even though this is not necessarily true of the glycerides of the fatty acids. In this instance, reference is made to the oxyalkylated derivatives in absence of a solvent. Since esterification is best conducted in a homogeneous system, it is our preference to add xylene, or even a higher boiling solvent such as mesitylene, cymene, tetralin, or the like, and conduct esterification in such consolute mixture. It is not necessary to add all the fatty acid at one time. One may add a quarter or half the total amount to be esterified and after such portion of the reactant has combined, then add more of the fatty acid. The solubility of the fatty acid, of course, increases as the hydroxyl radical is replaced by an ester radical. This is also true if one resorts to trans-esterification or cross-esterification with the glyceride or low molal alcohol ester.

Our preference is to have present a substantial amount of xylene or higher boiling, Waterinsoluble solvent, and to distill under a reflux condenser arrangement, so that water resulting from esterification is volatilized and condensed, along with the xylene vapor in a suitably arranged trap. The amount of xylene employed is approximately equal to one-half the weight of the mixed reactants. The water should be removed from the trap, either manually or automatically, and the xylene returned continuously for further distillation. Such reaction is hastened if a small amount of dry hydrochloric acid gas is continuously injected into the esterification mixture. When the reaction is complete the xylene is removed by distillation. Small amounts of unreacted fatty acid can be converted into the methyl or ethyl ester and removed by vacuum distillation, or permitted to remain. For example, an excess of anhydrous ethyl alcohol may be added, and reacted so as to esterify any residual fatty acid and then such excess of ethyl alcohol may be distilled off as 95% of alcohol-% of water mixture, and thus the water resulting from esterification with the alcohol can be removed. Although any residual fatty acid can be eliminated in the manner above described, this is of limited importance, except if one were preparing a drying oil fatty acid derivative which would ultimately find use in varnish production. In such instances, elimination of all fatty acid is important to give enhanced alkali resistance. 1% of conventional sulfonic acids such as paratoluene sulfonic acid may be employed as catalysts, especially if dried CO2 gas is employed instead of dried HCl gas.

However, even Where the amount of fatty acid employed is stoichiometrically equal to the hydroxyl radicals present, we have not found it desirable to take any undue precaution to eliminate any residual fatty acid. As a matter of fact, numerous examples include the present one and. those subsequently described which yield partial or fractional esters in which there is present residual hydroxyl radicals. Under such circumstances there is substantially no free fatty acid radicals present and the products obtained by partial esterification instead of complete esterification.

As a specific example, 600 grams of the xylenecontaining oxyalkylated resin identified as 1282) were refluxed with 75 grams of drastically-oxidized ricinoleic acid, along with 200 grams of added xylene and 20 gramsof para-toluene sul ionic acid. The reflux temperature was 142 C.; refluxing continued for 4 hours until 5 grams of water were evolved.

Example 20 The same procedure was followed as in Example 1c, preceding, except that the amount of drastically-oxidized castor oil fatty acid employed was suflicient to convert one-half of the polyglycol radicals into ester form.

As a specific example, 490 grams of the xylenecontaining resin identified as 1271) were reacted with grams of drastically-oxidized ricinoleic acid, following the procedure of Example 10, until 9 grams of water were evolved.

Example 30 The same procedure was followed as in example 1c, preceding, except that the amount of drastically-oxidized castor oil fatty acid employed was sufficient to convert three-fourths of the polyglycol radicals into ester form.

As a specific example, 490 grains of the xylenecontaining oxyalkylated resin identified as 11112 were reacted with 225 grams of drastically-oxidized ricinoleic acid, following the procedure of Example 10, for 6 hours until 15 grams of water were evolved.

Example 40 The same procedure was followed as in Example in to Example 40, preceding, except that the oxyalkylated derivatives, instead of being the ones exemplified under the headings Examples 10 to 40, were selected from some of the others previously described in detail elsewhere in the list of examples designated by the small letter 1).

As a specific example, 776 grams of the xylenecontaining oxyalkylated resin identified as 10Gb were mixed with 200 grams of drastically-oxidized ricinoleic acid along with 200 grams of added xylene and 20 grams of para-toluene sulfonic acid. The mixture was refluxed at l41.5 C. for approximately 5 hours until 16.3 grams of water had been eliminated.

Example 60 The same procedure was fail lowed as in Examples ie to 40, preceding, except that the oxyalkylated derivatives, instead of being the ones exemplified under the headings Examples 10 to 40, were selected from some of the others previously described in detail elsewhere in the list of examples designated by the small letter 1).

As a specific example 635 grams of the xylenecontaining oxyalkylated resin identified as 11512 were mixed with 290 grams of drastically-oxidized ricinoleic acid along with 200 grams of added xylene and 18.5 grams of para-toluene sulfonic acid. The mixture was refluxed for 6 hours at 147 C. with elimination of 17 grams of water.

Example 70 The same procedure was followed as in the pre- 

1. AN ESTER IN WHICH THE ACYL RADICAL IS THAT OF THE FATTY ACID OF BLOWN CASTOR OIL, AND THE ALCOHOLIC RADICALIS THAT OF CERTAIN HYDROPHILE POLYHYDRIC SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE PHENOLALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND HAVING ONE FUNCTIONAL GROUP REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALLY GREATER THAN TWO; SAID PHENOL BEING OF THE FORMULA 